CN1498951A - Lube compsn. - Google Patents
Lube compsn. Download PDFInfo
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- CN1498951A CN1498951A CNA2003101029526A CN200310102952A CN1498951A CN 1498951 A CN1498951 A CN 1498951A CN A2003101029526 A CNA2003101029526 A CN A2003101029526A CN 200310102952 A CN200310102952 A CN 200310102952A CN 1498951 A CN1498951 A CN 1498951A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/74—Noack Volatility
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Abstract
Lubricating oil compositions containing a major amount of oil of lubricati ng viscosity, an oil soluble molybdenum compound in an amount providing the composition with from 0.001 to 0.1 mass % molybdenum, an oil soluble copper antioxidant in an amount providing the composition with from 0.001 to 0.02 mass % copper to said composition, and an amount of metal hydrocarbyl dithiophospha te providing the composition with from 100 to 550 ppm phosphorus.
Description
The present invention relates to lubricating oil composition.More particularly, the present invention relates to present the lubricating oil composition of the low-phosphorous and sulphur content of improving oxidation-resistance.
Background of invention
The lubricating oil composition that is used for lubricated oil engine contains the mixture and the additive that is used for improving oily performance characteristic of lubricant viscosity base oil or this class oil.For example additive can be used to improve detergency, reduces engine scuffing, stability to heat and oxygenizement is provided, reduces oil consumption, suppresses its dispersion agent effect of burn into and reduce frictionloss.Some additives can provide multiple efficacies such as dispersion agent/viscosity modifier.Other additives can have disadvantageous effect to another characteristic when improving a certain characteristic of lubricating oil.Therefore for a kind of lubricating oil with best overall is provided, the institute that just need characterize and understand various additives is influential, carefully weighs content of additive in the lubricating oil.
For improving low temperature air valve machine members performance, conventional lubrication oil is to prepare with a kind of anti-wear agent.Hydrocarbyl dithiophosphoric acid metal-salt, particularly zinc dialkyl dithiophosphate (ZDDP) are the main wear agent that is used for internal combustion (IC) engine lubricating oil.ZDDP can provide good abrasion protection effect at lower cost and also play anti-oxidant action.But some signs show that the phosphorus in the lubricating oil can shorten the useful life of automotive exharst gas catalyst.Therefore industrially limit institute's phosphorus content in the lubricating oil is existing.Estimate that the new grade standard (ILSAC GF-4) that proposes will require to be no more than in the processed oil P of 0.08 weight % and the S of 0.5 weight %, estimate that following grade standard will require the phosphorus content of lubricating oil further to be reduced to 0.06 weight %.
US patent 5346635 and 5439605 has been described the lubricating oil that does not have phosphorous wear preventive additive fully, it contains the compounding mixture that agent, ash-free antiwear agent/extreme-pressure additive, oxidation inhibitor, metal detergent and polymer-type viscosity modifier and FLOW IMPROVERS are lowered in ashless friction, it is said that said composition can provide acceptable performance.These compositions also can comprise and contain molybdenum additives as friction improver.
Except that containing other special and necessary additive, contained ZDDP amount can provide 600ppm or lower phosphorus, also contains molybdenum base friction improver simultaneously in the described separately lubricating oil composition of WO96/37582 and EP 0855437.
Propose in many patents and article (for example the US patent 4164473,4176073,4176074,4192757,4248720,4201683,4289635 and 4479883), soluble molybdenum compounds is suitable as lubricating oil additive.Particularly molybdenum compound can make fuel economy, comprise that short-term and long-term economic (being the fuel economy retentivity) are improved in the engine (being respectively the engine of spark and compression igniting) that with gasoline or diesel oil is fuel.
Oil-soluble copper compounds is known effective oxidation inhibitor, described in US patent 4867890.
Preferably preparation can under the conditions of not using a large amount of expensive ashless (no metal) oxidation inhibitor, provide can accept oxidation-resistance subtract phosphorus lubricating oil.
Summary of the invention
According to the present invention, a kind of lubricating oil composition is provided, comprise the lubrication viscosity oil of main amount, a kind of soluble molybdenum compounds that is enough to offer composition 0.001-0.10 quality % molybdenum amount and a kind ofly be enough to offer the oil-soluble copper oxidation inhibitor of composition from about 0.001-0.02 quality % copper amount, described composition contains the hydrocarbyl dithiophosphoric acid metal-salt such as the ZDDP that the phosphorus of 100-550ppm can be introduced the lubricating oil composition amount.
Preferred lubricating oil composition contains the sulphur that is not more than 0.5 weight %.
Preferred lubricating oil composition does not contain the ashless oxidation inhibitor of (be less than 1 weight %, preferably be less than 0.5 weight %, more preferably 0-0.25 weight %) substantially.
Viscosity under 100 ℃ of the also preferred lubrication viscosity oils is at about 4.0-5.5 millimeter
2Between/second (centistoke) and/or the Noack volatility of lubricating oil composition (oil for preparing fully) be not more than 15 weight %.
The present invention is based on following discovery: in the lubricating oil composition of more a spot of ZDDP preparation molybdenum compound being used in combination with copper compound to provide beat all collaborative antioxidant effect.
The description of preferred embodiment
Market is acceptable a fine overall performance in order to provide cheaply, the product of oxidation-resistance particularly, lubricating oil composition of the present invention comprises the lubrication viscosity oil of main amount, a certain amount of, the dialkyl phosphorodithioic acid metal-salt of 200-550ppm (quality) phosphorus amount preferably can be provided, a kind of molybdenum compound that can offer composition 0.005-0.1 quality % molybdenum amount, with a kind of oil-soluble copper oxidation inhibitor that can offer composition from about 0.001-0.02 quality % copper amount, wherein all mass percents and ppm are based on that the total mass of lubricating oil composition or processed oil calculates.
Be applicable to that the lubrication viscosity oil of content of the present invention is selected from the blending base oil of I class, II class or III class, IV class or V class base-material or above-mentioned base-material.In general, the range of viscosities under 100 ℃ of this class oil is from about 2 millimeters
2/ second (centistoke) is to about 40 millimeters
2/ second, preferably the limiting viscosity under 100 ℃ is from about 4.0 millimeters
2/ second is to about 5.5 millimeters
2Base-material or the base material mixture of/second.The volatility of further preferred base-material and base material mixture (Noack test determination (press the step of ASTMD5880, measures 250 ℃ of heating oily mass percents of evaporating after 1 hour down)) less than 15%, be more preferably less than 12%, most preferably less than 10%.At most preferred oil aspect fuel economy retentivity and the low temperature air valve parts resistance to abrasion two be:
(a) blending base oil of III class, IV class or V class base-material and I class or II class base-material, wherein the viscosity index of composition is at least 110; And
(b) blending base oil of III class, IV class or V class base-material and III class, IV class and/or V class base-material, wherein the viscosity index of composition is about 120-140.
American Petroleum Institute (API) (API) publication of the definition of base-material of the present invention or base oil and in December, 1996 promulgation " engine oil permission and Verification System (Engine Oil Licensing andCertification System) " industrial service department (Industry Services Department), the 14 edition, the definition described in December, 1998 appendix 1 is identical.Described open source literature is classified as follows base oil:
(a) I class base-material contains less than 90% stable hydrocarbon and/or greater than 0.03% sulphur, and its viscosity index is more than or equal to 80 and less than 120.
(b) II class base-material contains more than or equal to 90% stable hydrocarbon and is less than or equal to 0.03% sulphur, and its viscosity index is more than or equal to 80 and less than 120.
(c) III class base-material contains more than or equal to 90% stable hydrocarbon and is less than or equal to 0.03% sulphur, and its viscosity index is more than or equal to 120.
(d) IV class base-material is polyalphaolefin (PAO).
(e) V class base-material comprises all not other base-materials within I, II, III or IV class.
Table 1 base-material analytical procedure
| Character | Test method |
| Stable hydrocarbon | ????ASTM?D2007 |
| Viscosity index | ????ASTM?D2270 |
| Sulphur | ????ASTM?D2622 |
| ????ASTM?D4294 | |
| ????ASTM?D4927 | |
| ????ASTM?D3120 |
Dialkyl phosphorodithioic acid metal-salt anti-wear agent comprises that metal is the dialkyl phosphorodithioic acid metal-salt of basic metal or alkaline-earth metal or aluminium, lead, tin, molybdenum, manganese, nickel or copper.What be most commonly used to lubricating oil is zinc salt.Although be expressed as ZDDP in the following description of this invention book, based on the dialkyl phosphorodithioic acid metal-salt of other metal also can think the equivalence.
Dialkyl phosphorodithioic acid metal-salt can prepare by known technology, normally with one or more alcohol or phenol and P
2S
5Reaction at first forms dialkyl phosphorodithioic acid (DDPA), then the DDPA that forms is neutralized with zn cpds.For example, can make phosphorodithioic acid by the reaction of primary alconol and secondary alcohol mixture.Perhaps, can prepare wherein a kind of alkyl that connects is that sechy-drocarbyl character and alkyl that other kind connects are the multiple phosphorodithioic acid of uncle's alkyl character fully fully.For the preparation zinc salt, can use any neutrality or basic zinc compound, but the most frequently used be oxide compound, oxyhydroxide and carbonate.Commercial additive contains excess zinc usually, because used excessive basic zinc compound in neutralization reaction.
Preferred dialkyl zinc dithiophosphate is oil-soluble dialkyl dithiophosphate, can be represented by the formula:
Wherein R and R ' can be the identical or different alkyl that contains 1-18, preferred 2-12 carbon atom, comprise the group such as alkyl group, alkenyl, aryl, aralkyl, alkaryl and cyclic aliphatic base.Particularly preferred group as R and R ' is the alkyl of 2-8 carbon atom.For example these groups can be ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, amyl group, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylbenzene base, cyclohexyl, methylcyclopentyl, propenyl, butenyl.For obtaining oil soluble, the total carbon atom number in the dithiophosphates (being R and R ') is about 5 or higher usually.Therefore, dialkyl zinc dithiophosphate (ZDDP) can comprise zinc dialkyl dithiophosphate.The zinc dialkyl dithiophosphate compound can be uncle's zinc, secondary zinc or their mixture.
In lubricating oil composition of the present invention, the amount of ZDDP (or other dialkyl phosphorodithioic acid metal-salt) is limited to and can obtains advantageous results and still can observe in the scope of low-phosphorous laws and regulations requirement.For wear-resistant advantage that ZDDP is provided but the phosphorus amount is limited to minimum 100ppm and maximum 550ppm (quality) (pressing element phosphor calculates), the amount of ZDDP should be limited to from about 0.12 to about 0.7 weight %, preferably from about 0.24 to about 0.63 weight % (based on lubricating oil composition (processed oil) gross weight meter).
Lubricating oil composition of the present invention contains can be provided from about 0.001-0.1, preferably from the molybdenum compound or the combination molybdenum compound of about 0.005-0.05 quality % amount for composition.Can use any suitable deliquescent organic molybdenum that can in the lubricating oil composition that phosphorus content reduces, have abrasion resistance that has.Be applicable to that oil soluble of the present invention or oil-dispersing property molybdenum compound are generally the molybdenum additives form that comprises one or more oil soluble or oil-dispersing property molybdenum compound.In a preferred embodiment, molybdenum compound is molybdenum-sulphur compound.
Be applicable to that molybdenum-sulphur compound of the present invention can be monokaryon or polynuclear compounds, if compound is a multinuclear, then compound contains the molybdenum core that is made of sulphur substantially that be made of non-metallic atom such as sulphur, oxygen and selenium, preferred.For making molybdenum-sulphur compound is oil soluble or oil-dispersing property, has one or more part to be keyed on the molybdenum atom of compound.The keyed jointing method of part comprises as carry out the form of keyed jointing and the middle keyed jointing between covalent linkage and ionic bond under the situation of gegenion by electrostatic interaction.A plurality of parts in the same compound are keyed jointing by different way.For example, but part can the covalency keyed jointing and another part static keyed jointing.
Or each part single anion preferably, and the example of this class part is phosphorodithioic acid root, dithiocarbamic acid root, xanthan acid group, carboxylate radical, sulfo-xanthan acid group, phosphate radical and their alkyl, preferred alkyl derivative.Be under the situation of polynuclear compounds at molybdenum-sulphur compound for example, the molybdenum atom number is preferably greater than 1: 1 with the ratio that can give the single anion ligand number of compound oil soluble or oil-dispersing property in the nuclear core, as is at least 3: 2.
The oil soluble of molybdenum-sulphur compound or the dispersed influence that can be subjected to the total carbon atom number that exists in the part of all compounds.The total carbon atom number that exists in the alkyl of all compound parts generally should be at least 21, and 21-800 for example is as at least 25, at least 30 or at least 35.For example, the carbonatoms in each alkyl generally will between the 1-100, preferred 1-40 and the more preferably scope between the 3-20.
The example of molybdenum-sulphur compound comprises two nuclear molybdenum-sulphur compounds and three nuclear molybdenum-sulphur compounds.
Two nuclear molybdenum-sulphur compounds be that example can be represented by the formula:
R wherein
1To R
4Straight chain, side chain or the aromatic hydrocarbyl of 1-24 carbon atom of independent expression, and X
1To X
4Independently be selected from Sauerstoffatom and sulphur atom.R
1To R
4Four alkyl can be identical or differ from one another.
In a preferred embodiment, molybdenum-sulphur compound is oil soluble or oil-dispersing property three nuclear molybdenum-sulphur compounds.The example of three nuclear molybdenum-sulphur compounds is disclosed in WO98/26030, WO99/31113, WO99/66013, EP-A-1138752, EP-A-1138686 and european patent application 02078011.Molybdenum-sulphur compound preferably have (I) or (II) shown in the nuclear core of structure:
Or
Wherein the net charge of each nuclear core is+4
Three nuclear molybdenum-sulphur compounds are preferably used formula Mo
3S
kE
xL
nA
pQ
zExpression, wherein
K is at least 1 integer;
The E representative is selected from the non-metallic atom of oxygen and selenium;
X can be 0 or integer, preferred k+x is at least 4, more preferably at 4-10 scope such as 4-7, most preferably be 4 or 7;
The L representative can be given the part of molybdenum-sulphur compound oil soluble or oil-dispersing property, and preferred L is a single anion ligand;
N is the integer of 1-4 scope;
A representative other negatively charged ion except that L is if L is the anionic part;
P can be 0 or integer;
Q represents the sub-compound of neutral power supply; With
The scope of z is 0-5 and comprises the nonstoichiometry value.
Those skilled in the art will recognize that, want to form three nuclear molybdenum-sulphur compounds and must select suitable part (L) and other negatively charged ion (A), this depends on for example examines the sulphur that exists in the core and the atomicity of E, must be-12 by sulphur atom, E atom, the L that may exist and total anionic charge that A provided that may exist promptly.
The example of Q comprises water, alcohol, amine, ether and phosphine.It is believed that the sub-compound Q of power supply only is to exist for any empty hapto that fills up on three nuclear molybdenum-sulphur compounds.The example of A can be any valency, for example is monovalence or dianion, and comprises two sulphur roots, hydroxide radical, alkoxy radical, acid amides root and thiocyanate radical or their derivative, the two sulphur root negatively charged ion of preferred A representative.
Preferred L is a single anion ligand, as phosphorodithioic acid root, dithiocarbamic acid root, xanthan acid group, carboxylate radical, sulfo-xanthan acid group, phosphate radical and their alkyl, preferred alkyl derivative.When n is 2 or when higher, each part can be identical or different.In one embodiment of the invention, k is 4 or 7, and n is 1 or 2, and L is a single anion ligand, and p makes the electroneutral integer of compound according to the anionic charge number on the A, and x and z respectively do for oneself 0.In another embodiment, k is 4 or 7, and L is a single anion ligand, and n is 4, and p, x and z respectively do for oneself 0.
Molybdenum-sulphur nuclear core, for example above (I) and (II) shown in the nuclear core of structure can promptly have the part of the functional group of energy keyed jointing molybdenum atom more than to be interconnected to form oligopolymer by one or more polydentate ligand.Molybdenum-the sulfur additives that comprises this quasi-oligomer can be considered to belong in the scope of the invention.The example of other molybdenum compound comprises carboxylic acid molybdenum and molybdenum nitrogen complex, and the two all can cure.
Lubricating oil composition of the present invention contains can offer composition from about 0.001-0.02 quality %, preferably from the oil-soluble copper oxidation inhibitor of about 0.008-0.016 quality % amount copper (press elemental copper calculating).
The example of suitable cupric oxidation inhibitor comprises mentioned oil-soluble copper compounds among European publication EP 0024146B, EP0280579A, EP 0280580A and the US 4867890, and all disclosures are introduced this patent as a reference.For example, can form copper is synthetic with oil soluble or natural carboxylic acid's mantoquita transfer mixed in oil.The carboxylic acid that can be used to obtain suitable mantoquita comprises C
2-C
18Lipid acid (as acetate, stearic acid, palmitinic acid), unsaturated acid (as oleic acid), the di-carboxylic acid that branched carboxylic acids (as naphthenic acid, neodecanoic acid and the 2 ethyl hexanoic acid of molecular weight 200-500) and alkyl group, alkenyl replace (as the succsinic acid such as the polyisobutenyl succsinic acid of polyalkenyl replacement).In some cases, can be by acid anhydrides as obtaining suitable compounds by substituted succinyl oxide.
Copper oxidation inhibitor for example can be dithiocarbamic acid copper or phosphorodithioic acid copper.The antioxidant compound of other cupric and sulphur for example copper mercaptide, xanthogenic acid copper, sulfo-xanthogenic acid copper also is applicable to the present invention, the same sulfonic acid copper in addition that is suitable for, phenol copper (optional with its sulfuration) and acetylacetone copper.Can be used for other copper compound of the present invention is the high alkalinity copper compound.Example of this compounds and preparation method thereof is referring to US patent 4664822 and European patent 0425367A, and the content of these two pieces of documents is introduced this patent as a reference.Copper compound can be monovalence copper or cupric form.
Measure the amount of phosphorus, molybdenum and copper in any composition by the step of ASTM D5185.
Substantially do not contain in the preferred composition of the present invention (contain be less than about 1 weight %, preferably be less than 0.5 weight %, more preferably lack 0-0.25 weight %) ashless or claim no metal auxiliary antioxidant, typical commercial ashless oxidation inhibitor to comprise phenols and amine antioxidants.
Ashless phenolic antioxidant comprises hindered phenol, preferably has C
5-C
12The alkaline earth salt of the alkylphenol monothioester of alkyl group side chain, sulfuration nonyl phenol calcium (NPS), ashless oil soluble phenates and sulfuration phenates and phosphorus sulfuration or sulfuration hydrocarbon.
Ashless amine antioxidants comprises having at least two aryl directly to be connected in arylamine on the nitrogen.The oil soluble arylamine that typically has at least two aryl directly to be connected on the nitrogen of an amine contains 6-16 carbon atom.Amine can contain plural aryl.At least 3 of total aryl numbers, wherein two by covalent linkage or by an atom or group (as oxygen or sulphur, or-CO-,-SO
2-or alkylidene group) key and two directly link compound on the nitrogen of an amine and also regard as and have at least two aryl directly to be connected in arylamine on the nitrogen.Aromatic ring generally can be replaced by one or more substituting group that is selected from alkyl, cycloalkyl, alkoxyl group, aryloxy, acyl group, amido, hydroxyl and nitro.
Other additive can be introduced in the composition of the present invention, to satisfy the needs of actually operating.The example that can be included in the other additive in the lubricating oil composition of the present invention is ashless dispersant, become grey purification agent, metal antirusting agent, viscosity index improver, sanitas, defoamer and pour point reducer.Hereinafter will further go through some additives.
Dispersion agent can keep suspended state with the material that is insoluble to oil that forms because of oxygenizement in the use, therefore avoids the settling of mud cohesion and deposition or metallic surface.The dispersion agent that is applicable to content of the present invention comprises that scope is known nitrogenous ashless (no metal) dispersion agent, can effectively reduce sedimental formation in gasoline and the diesel motor use when it adds lubricating oil.This class ashless dispersant comprises an oil-soluble polymers long-chain skeleton that has the functional group that can help particles dispersed.This class dispersion agent generally has amine, alcohol, acyl or ester amine polarity partly to be connected on the polymer backbone, normally connects by abutment.Ashless dispersant for example can be selected from the monobasic of long chain hydrocarbon replacement and oil soluble salt, ester, amino ester, acid amides, inferior acid amides and the oxazoline of polycarboxylic acid or acid anhydrides, the thiocarboxylic acid salt derivative of long chain hydrocarbon, directly be connected with the long chain aliphatic hydrocarbon of polyamines part, also suitable by the Manny phase condensation product of long-chain substituted phenol and formaldehyde and polyalkylene polyamine condensation formation.
The consumption of dispersion agent is from about 0.5-10.0 weight %, preferably from about 1-3 weight % in the lubricating oil composition of the present invention.The polyisobutenyl succinimide dispersion agent is preferred, and wherein the Mn of polyisobutenyl is about 500-3000, preferred about 900-2500.Embodiment preferred is to use the polyisobutenyl succinimide dispersion agent of polyisobutene preparation, and the active isobutene polymer that has vinylidene olefinic end group then is to be made by the pure iso-butylene materials flow or the I materials flow of raffinating oil.Preferred these terminal vinylidene content that are called the polymkeric substance of high-activity polyisobutene (HR-PIB) are at least 65% for example 70%, and more preferably at least 80%, most preferably at least 85%.The preparation method of this polymkeric substance for example is described in U.S.4152499.HR-PIB is known, and HR-PIB can be at trade(brand)name Glissopal
TM(providing) and Ultravis by BASF AG
TM(being provided by BP-Amoco company) is commercial down.
Containing metal or to become the effect of grey purification agent be to reduce or remove settling to play acid neutralizing agent or rust-preventive agent effect simultaneously, thus reduce wear and corrode, prolong engine life.Purification agent generally includes a polar head and long-chain hydrophobic tail, and polar head comprises the metal-salt of acidic organic compound.Salt can contain substantially by stoichiometric metal, and in the case, they are described to Neutral salt or neutral salt usually, and its total basicnumber (TBN) (can measure by ASTM D2896 method) generally from 0 to 80.Can introduce a large amount of metal base by excess metal compound such as oxide compound or oxyhydroxide and sour gas such as carbon dioxide reaction.The high alkaline detergent that obtains comprise as metal base (as carbonate) micella outer field in and purification agent.The TBN of this class high alkaline detergent is 150 or higher, generally from 250-450 or higher.
Known purification agent comprises sulfonate, phenates, sulfuration phenates, thiophosphate, salicylate and naphthenate and other oil soluble carboxylate salt of oil soluble neutrality or overbased metal, particularly basic metal or alkaline-earth metal such as barium, sodium, potassium, lithium, calcium and magnesium.The most frequently used metal is calcium and magnesium, and the two all can exist in the used purification agent of lubricant, and the mixture of calcium and/or magnesium and sodium.Shi Yi metal detergent be TBN from the neutrality of 20-450 and high alkaline calcium sulfonate, TBN from 50-450 neutrality or high alkalinity phenol calcium and sulfation phenol calcium especially.
Preferred in the present invention high alkaline detergent, when using, its consumption is from about 0.5-5 weight % (based on the composition total weight meter).The total basicnumber of overbased sulfonate detergents is preferably between 150-450.Further preferred high alkaline detergent is a high alkaline calcium sulfonate.
Viscosity modifier (VM) work to give lubricating oil high-temp and cold operation.Used VM can be unifunctional or multi-functional.The representative example of the viscosity modifier that is suitable for is a polyisobutene, ethene and propylene copolymer, polymethacrylate, alkylmethacrylate polymer, the multipolymer of unsaturated dicarboxylic acid and vinyl compound, the multipolymer of vinylbenzene and acrylate and partially hydrogenated styrene/isoprene, phenylethylene/butadiene and isoprene/butadiene multipolymer, and partially hydrogenated divinyl and isoprene homopolymer.The multi-functional viscosity modifier of also setting up another the dispersion agent effect also is known.
Can use the rust-preventive agent that is selected from poly-(oxyalkylene) the many alcohol of non-ionic type and ester, poly-(oxyalkylene) phenol and anionic sulfonic acid alkanol ester.
Can use the additive that stops copper and plumbous bearing corrosion, but generally not need in the prescription of the present invention to use.This compounds generally is the thiadiazoles polysulfide that contains 5-50 carbon atom, their derivative and polymkeric substance thereof.1,3, the derivative of 4-thiadiazoles is exactly typical example as the compound that is described in US patent 2719125,2719126 and 3087932.Other similar substance description is in US patent 3821236,3904537,4097387,4107059,4136043,4188299 and 4193882.Other additive is the sulfo-and the polythio sulfinyl amine of thiadiazoles, as is described in the compound of UK patent specification 1560830.Benzotriazole derivatives also belongs to this class additive.When comprising these compounds in the lubricating oil composition, preferably its amount is no more than 0.2 weight % activeconstituents.
Can use a spot of emulsion splitter component.Preferred emulsion splitter component is described in EP330522, is to react acquisition by the adducts that oxirane and a kind of di-epoxide and polyol reaction are obtained.Emulsion splitter should use by the amount that is no more than 0.1 quality % activeconstituents.Suitable processing ratio is 0.001-0.05 quality %.
Pour point reducer claims the lubricating oil improving agent that flows again, and the minimum temperature that can make fluid flow or to topple over reduces.This class additive is well-known.Typical case's representative that can improve the additive of fluid low-temperature fluidity is fumaric acid C
8-C
18Dioxane alcohol ester/vinyl acetate copolymer and polymethacrylate etc.
The chemical compound lot that comprises the polysiloxane defoamer can provide the effect of inhibition foamy, as silicone oil or polydimethylsiloxane.
Available any mode is easily introduced each single additive of planting in the base-material.For example, every kind of component all can directly be added in base-material or the blending base oil by the method for it being disperseed with required concentration or be dissolved in base-material or the blending base oil.Such blending process can be carried out at normal temperatures or under heating up.
All additives that preferably will be except that viscosity modifier and pour point reducer are called in the concentrated solution of additive-package or the additive-package at this paper to be concocted, and then is blended in the base-material, makes finished lube.Generally be that preparation contains the concentrated solution of appropriate amount additive, can in final prescription, provide required concentration during with the lubricating base oils merging of convenient concentrated solution and pre-determined quantity.
Concentrated solution is preferably pressed disclosed method preparation among the U.S.4938880.Described patent disclosure make the method for the premixture of ashless dispersant and metal detergent, be under at least about 100 ℃, to concoct in advance.After this, premixture is cooled at least 85 ℃, adds other component then.
Final crankcase lubrication oil formula can use 2-20 quality %, preferred 4-18 quality %, most preferably from about concentrated solution or the additive-package of 5-17 quality %, and all the other are base-material.Composition can be used for crankcase oil (being bus engine oil, heavy duty diesel engine oil and the passenger vehicle diesel engine oil) prescription of spark-ignited and compression ignition engine.
Preferred lubricating oil composition of the present invention contains the sulphur that is not more than 0.5 weight %.
Can further understand the present invention with reference to following examples, unless otherwise noted, all percentage ratios wherein are the weight percentage of activeconstituents, and these embodiment comprise the present invention
Preferred embodiment.
Embodiment
Prepare following lubricating oil and carry out oxidation resistance test by step employing MHT-4 (middle high temperature-4) TEOST (test of the thermo-motor oil-proofness) method of ASTM 06335.Each lubricating oil sample contains identical mineral oil base-material, dispersion agent, purification agent, organic friction improver and the defoamer of equivalent.Each sample contains the ZDDP of 0.64 weight %, and the phosphorus content of 510ppm can be provided for each sample.Contain a certain amount of copper compound (cupric oleate), molybdenum compound (molybdenum dithiocarbamate) and auxiliary ashless oxidation inhibitor (sulfuration nonyl phenol or Sheng NPS).
The amount of copper compound and molybdenum compound is elemental copper and the weight of molybdenum % report to be introduced respectively.MHT-4 TEOST result is with the mg number report of gains (settling) weight.Lower gains weight is represented improved oxidation-resistance.It is 45mg that GF-3 lubricating oil specification standard allows ceiling value.The ceiling value that GF-4 lubricating oil specification standard is proposed is 25mg.
Table 2
| Embodiment | ????C1 | ????C2 | ????I1 | ????C3 | ????C4 | ????C5 |
| Cu (quality %) | ????0 | ????0.016 | ????0.008 | ????0.016 | ????0 | ????0 |
| Mo (quality %) | ????0 | ????0 | ????0.011 | ????0.011 | ????0 | ????0.019 |
| NPS (weight %) | ????0 | ????0 | ????0 | ????1.18 | ????1.18 | ????0 |
| Describe | Substrate | ????Cu | ????Cu/Mo | ????Cu/NPS | ????NPS | ????Mo |
| ?TEOST(mg) | ????68.9 | ????63.5 | ????46.9 | ????65.8 | ????63.7 | ????51.2 |
Example I 1 representative lubricating oil composition of the present invention.As shown in table 2 data, in the lubricating oil composition that reduces phosphorus content, the oxidation-resistance that is provided when molybdenum compound is used in combination with copper compound is better than the effect when using equivalent copper compound or molybdenum compound and molybdenum compound to be used in combination with ashless phenolic antioxidant respectively.
What should note a bit is that lubricating oil composition of the present invention comprises that the independent component that defines that mixing front and back chemical structure can be identical or different is independent component.Therefore, be to be understood that the various components of composition, necessary component and optional and conventional component can react under preparation, storage or working conditions condition, the present invention also at comprise can by or react resulting product by any this class.
The full content of all patents as herein described, article and other data is all introduced this specification sheets as a reference.In the top specification sheets principle of the present invention, preferred embodiment and operator scheme have been described.But, can not think that the invention that the applicant submitted to is only limited to disclosed specific embodiments, indefiniteness scheme because disclosed specific embodiments should be considered as exemplary.Under the prerequisite that does not deviate from spirit of the present invention, those skilled in the art can do various changes.
Claims (15)
1. lubricating oil composition, comprise main amount lubrication viscosity oil, can offer described composition 0.001-0.01 quality % molybdenum amount soluble molybdenum compounds, can offer the oil-soluble copper oxidation inhibitor of described composition 0.001-0.02 quality % copper amount and can offer the hydrocarbyl dithiophosphoric acid metal-salt of the phosphorus amount of described composition 100-550ppm.
2. the lubricating oil composition of claim 1, wherein said hydrocarbyl dithiophosphoric acid metal-salt is a zinc dialkyl dithiophosphate.
3. the lubricating oil composition of claim 1, the Noack volatility of wherein said composition is not more than 15 weight %.
4. the lubricating oil composition of claim 1 further comprises ashless dispersant.
5. the lubricating oil composition of claim 4, wherein said dispersion agent is a polyisobutenyl succinimide.
6. the lubricating oil composition of claim 1, wherein said copper oxidation inhibitor is cupric oleate.
7. the lubricating oil composition of claim 1, the viscosity of wherein said lubrication viscosity oil under 100 ℃ is 4.0 millimeters
2-5.5 millimeters of/seconds
2/ second.
8. the lubricating oil composition of claim 1, the oil of wherein said lubricating oil composition are II class oil, III class oil, IV class oil, V class oil or its mixture, or the mixture of I class oil and at least a II class oil, III class oil, IV class oil or V class oil.
9. the lubricating oil composition of claim 1, wherein said lubrication viscosity oil comprises IV class oil.
10. the lubricating oil composition of claim 1, wherein said molybdenum compound is an organic molybdenum.
11. the lubricating oil composition of claim 10, wherein said organic molybdenum is a molybdenum dithiocarbamate.
12. the lubricating oil composition of claim 1, wherein said composition does not contain ashless oxidation inhibitor substantially.
13. the lubricating oil composition of claim 1 further comprises at least a high alkaline metal detergent.
14. the lubricating oil composition of claim 13, wherein said at least a high alkaline metal detergent are high alkalinity calcium purification agents.
15. the lubricating oil composition of claim 1, wherein said composition contains the sulphur that is not more than 0.5 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/285,122 | 2002-10-31 | ||
| US10/285,122 US20040087452A1 (en) | 2002-10-31 | 2002-10-31 | Lubricating oil composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1498951A true CN1498951A (en) | 2004-05-26 |
Family
ID=32093551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2003101029526A Pending CN1498951A (en) | 2002-10-31 | 2003-10-30 | Lube compsn. |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20040087452A1 (en) |
| EP (1) | EP1416034A1 (en) |
| JP (1) | JP2004149799A (en) |
| CN (1) | CN1498951A (en) |
| CA (1) | CA2447567A1 (en) |
| SG (1) | SG114637A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146550A (en) * | 2015-04-02 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | The metal salt derivatives of anacardol and derivative base D2EHDTPA thereof, its preparation method and application |
| CN110506099A (en) * | 2017-03-31 | 2019-11-26 | 协同油脂株式会社 | Lubricant oil composite |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6080489B2 (en) * | 2005-01-07 | 2017-02-15 | Ｊｘエネルギー株式会社 | Lubricating base oil |
| WO2006073198A1 (en) | 2005-01-07 | 2006-07-13 | Nippon Oil Corporation | Lubricant base oil, lubricant composition for internal combustion engine and lubricant composition for driving force transmitting device |
| JP5289670B2 (en) | 2005-06-17 | 2013-09-11 | 出光興産株式会社 | Engine oil composition |
| WO2007125587A1 (en) * | 2006-04-27 | 2007-11-08 | Ibiden Co., Ltd. | Additive for engine oil, engine oil and method of exhaust gas purification |
| US20080236538A1 (en) * | 2007-03-26 | 2008-10-02 | Lam William Y | Lubricating oil composition for improved oxidation, viscosity increase, oil consumption, and piston deposit control |
| EP2045314B1 (en) * | 2007-10-04 | 2017-11-08 | Infineum International Limited | An overbased metal sulphonate detergent |
| US20090163392A1 (en) * | 2007-12-20 | 2009-06-25 | Boffa Alexander B | Lubricating oil compositions comprising a molybdenum compound and a zinc dialkyldithiophosphate |
| JP2012046555A (en) * | 2010-08-24 | 2012-03-08 | Adeka Corp | Lubricant composition for internal combustion engine |
| US9670432B2 (en) * | 2013-02-24 | 2017-06-06 | Saeed Mir Heidari | Biological method for preventing rancidity, spoilage and instability of hydrocarbon and water emulsions and also increase the lubricity of the same |
| WO2015172846A1 (en) * | 2014-05-16 | 2015-11-19 | Ab Nanol Technologies Oy | Additive composition for lubricants |
| FI3798287T3 (en) * | 2019-09-27 | 2023-11-02 | Ab Nanol Tech Oy | Use of organometallic salt compositions for alleviating the formation of white etching cracks |
| CN113913228B (en) * | 2021-11-12 | 2022-11-22 | 福建优立盛油脂有限公司 | Antioxidant composition for lithium-based lubricating grease |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2056482A (en) * | 1979-08-13 | 1981-03-18 | Exxon Research Engineering Co | Lubricating oil compositions |
| US4705641A (en) * | 1986-09-15 | 1987-11-10 | Exxon Research And Engineering Company | Copper molybdenum salts as antioxidants |
| US5281347A (en) * | 1989-09-20 | 1994-01-25 | Nippon Oil Co., Ltd. | Lubricating composition for internal combustion engine |
| ES2139756T3 (en) * | 1993-09-13 | 2000-02-16 | Infineum Usa Lp | LUBRICATING COMPOSITIONS WITH IMPROVED ANTIOXIDING POWER. |
| CA2163813C (en) * | 1994-12-20 | 2007-04-17 | Elisavet P. Vrahopoulou | Lubricating oil composition comprising metal salts |
| US6358894B1 (en) * | 1996-12-13 | 2002-03-19 | Infineum Usa L.P. | Molybdenum-antioxidant lube oil compositions |
| JP2000186293A (en) * | 1998-12-21 | 2000-07-04 | Tonen Corp | Diesel engine lubricating oil composition |
| US6174842B1 (en) * | 1999-03-30 | 2001-01-16 | Ethyl Corporation | Lubricants containing molybdenum compounds, phenates and diarylamines |
| DE60117311T2 (en) * | 2000-03-29 | 2006-08-03 | Infineum International Ltd., Abingdon | Organic molybdenum complex-containing lubricant compositions |
| US6500786B1 (en) * | 2001-11-26 | 2002-12-31 | Infineum International Ltd. | Lubricating oil composition |
| US6723685B2 (en) * | 2002-04-05 | 2004-04-20 | Infineum International Ltd. | Lubricating oil composition |
| US6642188B1 (en) * | 2002-07-08 | 2003-11-04 | Infineum International Ltd. | Lubricating oil composition for outboard engines |
-
2002
- 2002-10-31 US US10/285,122 patent/US20040087452A1/en not_active Abandoned
-
2003
- 2003-09-18 EP EP20030255866 patent/EP1416034A1/en not_active Withdrawn
- 2003-10-30 SG SG200306450A patent/SG114637A1/en unknown
- 2003-10-30 CN CNA2003101029526A patent/CN1498951A/en active Pending
- 2003-10-30 JP JP2003370836A patent/JP2004149799A/en active Pending
- 2003-10-31 CA CA002447567A patent/CA2447567A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146550A (en) * | 2015-04-02 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | The metal salt derivatives of anacardol and derivative base D2EHDTPA thereof, its preparation method and application |
| CN106146550B (en) * | 2015-04-02 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | Metal salt derivatives, preparation method and the application of anacardol and its derivative base thiophosphoric acid |
| CN110506099A (en) * | 2017-03-31 | 2019-11-26 | 协同油脂株式会社 | Lubricant oil composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004149799A (en) | 2004-05-27 |
| US20040087452A1 (en) | 2004-05-06 |
| SG114637A1 (en) | 2005-09-28 |
| EP1416034A1 (en) | 2004-05-06 |
| CA2447567A1 (en) | 2004-04-30 |
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